1. Field of the Invention
This invention relates to a process for producing an unsaturated carboxylic acid from an alkane. In particular, this invention relates to a process for producing acrylic acid from propane by a single step vapor phase oxidation reaction.
2. Description of the Prior Art
The production of an unsaturated carboxylic acid, such as acrylic acid or methacrylic acid, is conventionally done by catalytically reacting an olefin, such as propylene or isobutylene, with oxygen to form an alkenylaldehyde, such as acrolein or methacrolein, which is subsequently catalytically reacted with oxygen. Alkanes, such as propane, have advantages of cost and of availability over olefins. Furthermore, a one step process would have advantages over the present commercial process.
There are instances of producing acrylic acid and other unsaturated carboxylic acids from propane and other alkanes in a one step vapor phase catalytic oxidation reaction. U.S. Pat. No. 5,380,933 discloses a method for producing an unsaturated carboxylic acid, such as acrylic acid, with a mixed metal oxide catalyst containing molybdenum, vanadium, tellurium, and at least one of niobium, tantalum, tungsten, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, antimony, bismuth, boron, indium and cerium. Neither gallium, silver nor gold was disclosed as a component of the catalyst. There was no suggestion to select antimony over the other possible components for the catalyst. Tellerium is a necessary component of this prior art catalyst.
Japanese published patent application H10-57813 discloses a metal oxide catalyst of molybdenum, vanadium, tellurium and/or antimony and an element selected from niobium, tantalum, tungsten, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, bismuth, boron, indium, phosphorus, rare earth elements, alkali metals, alkali-earth metals. Neither gallium, silver nor gold was disclosed as a component of the catalyst. There was no suggestion to select bismuth over the other possible components for the catalyst.
Japanese published patent application H10-45664 discloses a catalyst of oxides of molybdenum, vanadium, antimony and an element selected from niobium, tantalum, tungsten, titanium, zirconium, chromium, iron, manganese, ruthenium, cobalt, rhodium, nickel, palladium, platinum, boron, indium, alkali metals, alkaline earth metals, and rare earth elements. Neither gallium, bismuth, silver nor gold was disclosed as a component of the catalyst.
European published patent application 0 962 253 discloses a catalyst having oxides of molybdenum, tungsten, iron, niobium, tantalum, zirconium, ruthenium and mixtures thereof; vanadium, cerium, chromium and mixtures, thereof; tellurium, bismuth, antimony, selenium, and mixtures thereof; and niobium, tantalum, tungsten, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhenium, nickel, palladium, platinum, antimony, bismuth, boron, indium, cerium and mixtures thereof. Neither gallium, silver nor gold was disclosed as a component of the catalyst. There was no suggestion to select antimony or bismuth over the other possible components for the catalyst.
Japanese issued patent no. 10-120,617 discloses a supported catalyst having oxides of molybdenum, vanadium, antimony, one of niobium, tantalum, tin, tungsten, titanium, nickel, iron, chromium or cobalt, and at least one of sodium, potassium, rubidium, cesium, phosphorus and arsenic. Neither gallium, bismuth, silver nor gold was disclosed as a component of the catalyst.
Japanese published patent application H6-218286 disclosed a heteropolyacid catalyst having oxides of phosphorus, molybdenum, vanadium, at least one of arsenic and antimony, and at least one of tin, lead, cerium, cobalt, iron, zirconium, thorium, tungsten, germanium, nickel, rhenium, bismuth, chromium, boron, magnesium, calcium, barium, strontium, selenium, tellurium, silver, aluminum, zinc, copper, titanium, potassium, rubidium, cesium and thallium. Neither gallium, gold nor niobium was disclosed as a component of the catalyst. There was no suggestion to select antimony and silver over the other possible components for the catalyst.
U.S. Pat. Nos. 6,160,162 and 6,114,278 disclose a calcined catalyst having molybdenum, vanadium, gallium, palladium, niobium and at least one of lanthanum, tellurium, germanium, zinc, silicon, indium and tungsten. Neither antimony, bismuth, gold nor silver was disclosed as a component of the catalyst.
U.S. Pat. Nos. 5,994,580 and 6,060,422 discloses a process for producing acrylic acid from propane and oxygen with a mixed metal oxide catalyst containing molybdenum, vanadium, antimony and at least one of niobium, tantalum, tin, tungsten, titanium, nickel, iron, chromium and cobalt. Neither gallium, bismuth, silver nor gold was disclosed as a component of the catalyst.
Japanese patent no. 11114418 discloses a catalyst having oxides of niobium, molybdenum, antimony, at least one of phosphorus, arsenic, boron, silicon and germanium and at least one of potassium, cesium, rubidium, calcium, magnesium, tellurium, chromium, manganese, iron, cobalt, nickel, copper, silver, lead, bismuth, aluminum, gallium, indium, tin, zinc, lanthanum, cerium, yttrium, tungsten, tantalum, ruthenium, rhodium, palladium, platinum, iridium, osmium, rhenium and hafnium. Neither gold nor vanadium was disclosed as a component of the catalyst. There was no suggestion to select gallium, bismuth or silver over the other possible components for the catalyst.
Chinese patent application 1,159,960 discloses bismuth based catalysts with vanadium, niobium, or tantalum and chromium, molybdenum or tungsten, optionally with lithium, sodium, potassium, copper, silver or gold. Neither antimony nor gallium disclosed as a component of the catalyst. There was no suggestion to select gold or silver over the other possible components for the catalyst.
U.S. Pat. No. 4,339,355 discloses a catalyst having molybdenum, vanadium and niobium with chromium, copper, manganese or yttrium. Neither antimony, gallium, gold nor silver was disclosed as a component of the catalyst.
U.S. Pat. No. 6,252,122 discloses a catalyst having molybdenum, bismuth and phosphorus with vanadium, niobium, tantalum, chromium, tungsten, gallium, cerium or lanthanum; lithium, sodium, potassium, rubidium, cesium, copper, silver, gold, palladium or platinum; tin, lead, antimony, bismuth, tellurium, iron, cobalt or nickel; and silicon, aluminum, titanium or zirconium. There was no suggestion to select gallium or gold over the other possible components for the catalyst.
U.S. Pat. No. 5,807,531 discloses a catalyst having molybdenum and vanadium with tungsten, niobium, titanium, zirconium, hafnium, tantalum, chromium, silicon or germanium. Neither antimony, gallium, bismuth, silver nor gold was disclosed as a component of the catalyst.
Japanese patent application no. 246,108 (2000) discloses a catalyst having molybdenum, vanadium and antimony with niobium or tantalum and silver, zinc, tin, lead, arsenic, copper, thallium or selenium. Neither gallium, bismuth nor gold was disclosed as a component of the catalyst. There was no suggestion to select silver over the other possible components for the catalyst.
U.S. Pat. Nos. 6,114,278 and 6,160,162 disclose a catalyst for producing acrylic acid by catalytic vapor phase partial oxidation of propane in one stage. The catalyst contains molybdenum, vanadium, gallium, palladium, niobium and at least one of lanthanum, tellurium, germanium, zinc, silicon, indium or tungsten. There was no disclosure of antimony, bismuth, silver or gold as a component of the catalyst.
PCT/EP01/06821 (WO01/98246) discloses a method of producing acrylic acid with a catalyst containing molybdenum, vanadium and tellurium or antimony and at least one of niobium, tantalum, tungsten, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, gallium, platinum, bismuth, boron or cerium. Neither silver nor gold was disclosed as a component of the catalyst of this invention. There was no suggestion to select gallium and antimony over the other possible components. There was no working example of a catalyst containing antimony or gallium.
U.S. Pat. No. 6,383,978 discloses a catalyst for vapor phase oxidation of an alkane to an unsaturated carboxylic acid and for vapor phase ammoxidation of an alkane to an unsaturated nitrile. The catalyst contains molybdenum, vanadium, at least one of tellurium, antimony, tin, germanium or bismuth, at least one of niobium, tantalum, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, platinum, boron, indium, arsenic, lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, hafnium, lead, phosphorus, promethium, europium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, lanthanum, scandium, gold, silver, palladium, gallium, praseodymium, rhenium, iridium, neodymium, yttrium, samarium, terbium, tungsten, cerium, copper or zinc, and at least one of selenium or bismuth. There was no suggestion to select gallium, gold, silver and antimony over the other possible components. The catalyst of this invention must contain selenium or bismuth.
U.S. Pat. No. 6,407,280 discloses a catalyst for oxidation of propane or isobutane to acrylic acid or methacrylic acid. The catalyst contains molybdenum or tungsten; vanadium or cerium; tellurium, antimony or selenium; optionally at least one of niobium, tantalum, titanium, aluminum, zirconium, chromium, manganese, iron ruthenium, cobalt, rhodium, nickel, platinum, antimony, bismuth, boron, indium, arsenic, germanium, tin, lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, hafnium, lead, phosphorus, promethium, europium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium; and at least one of nickel, palladium, copper, silver or gold. Gallium was not disclosed as a component of the catalyst of this invention. There was no suggestion to select antimony over the other possible components. There was no working example of a catalyst containing antimony or gallium.
U.S. Pat. No. 6,403,525 disclosed a catalyst for the oxidation or ammoxidation of alkanes. The catalyst contains molybdenum, vanadium, at least one of tellurium, antimony, tin, germanium or bismuth, at least one of niobium, tantalum, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, platinum, boron, arsenic, lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, hafnium, lead, phosphorus, promethium, europium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, lanthanum, scandium, gold, silver, palladium, gallium, praseodymium, rhenium, iridium, neodymium, yttrium, samarium, thorium, tungsten, cerium, copper, or zinc and at least one of indium or rhenium. There was no suggestion to select gallium, bismuth, silver or gold and antimony over the other possible components. The catalyst of this invention must contain indium or rhenium.
Catalyst with similar compositions have been used for processes other than those for producing acrylic acid and other unsaturated carboxylic acids from propane and other alkanes in a one step vapor phase catalytic oxidation reaction.
U.S. Pat. No. 4,250,346 discloses a catalyst for catalytically oxyhydrogenating ethane to ethylene, said catalyst having molybdenum with chromium, manganese, niobium, tantalum, titanium, vanadium or tungsten or bismuth, cerium, cobalt, copper, iron, potassium, magnesium, nickel, phosphorus, lead, antimony, silicon, tin, thallium or uranium. Neither gallium, silver nor gold was disclosed as a component of the catalyst. There was no suggestion to select vanadium, niobium and antimony over the other possible components for the catalyst.
Japanese patent application no. 10-310,539 discloses a catalyst to form propylene from propane, said catalyst having molybdenum, vanadium and niobium. Neither gallium, bismuth, silver nor gold was disclosed as a component of the catalyst.
U.S. Pat. No. 6,043,185 disclosed a catalyst for making acrylonitrile or methacrylonitrile by vapor phase catalyzed reaction of propane or isobutane with oxygen and ammonia. This catalyst contained molybdenum, vanadium, antimony, gallium and at least one of from arsenic, tellurium, selenium, niobium, tantalum, tungsten, titanium, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, boron, indium, cerium, rhenium, iridium, germanium, tin, bismuth, yttrium, praseodymium, an alkali metal and an alkaline earth metal, a is 1; b is 0.0–0.99; c is 0.01–0.9; d is 0.01–0.5; e is 0.0–1.0; and x is determined by the oxidation state of the cations present and the catalyst is preferably free of tellurium (less than 0.01). For a feed of propane, ammonia, oxygen, nitrogen and water, a comparative example without gallium showed selectivities to acrylonitrile of 50.7% and to acrylic acid of 1.5% and examples of the gallium promoted catalyst showed selectivities to acrylonitrile of 45.8–60.3% and to acrylic acid of 0.4 to 3.4%. Neither silver nor gold was disclosed as a component of the catalyst. There was no suggestion to select bismuth over the other possible components for the catalyst.
U.S. Pat. No. 6,036,880 discloses oxidation of propane with a catalyst containing molybdenum, vanadium, niobium and tellurium and/or antimony in which the niobium was dissolved in a particular amount of dicarboxylic acid. Gallium, bismuth, silver and gold were not disclosed as components of the catalyst.
U.S. Pat. Nos. 5,973,186 and 6,080,882 discloses a catalyst for producing an unsaturated nitrile from an alkane by ammoxidation which contains molybdenum, vanadium, niobium, either tellurium or antimony, and, optionally, tantalum, tungsten, titanium, zirconium, hafnium, iron, chromium, manganese, rhenium, ruthenium, cobalt, rhodium, nickel, palladium, osmium, iridium, platinum, copper, silver, zinc, cadmium, boron, aluminum, gallium, indium, thallium, germanium, tin, lead, phosphorus, bismuth, selenium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, alkali metals and alkaline earth metals. There was no suggestion to select gallium, bismuth or silver over the other possible components. Gold was not disclosed as a component of the catalyst.
U.S. Pat. No. 6,063,728 disclosed an ammoxidation catalyst for producing acrylonitrile or methacrylonitrile. The catalyst contains molybdenum, vanadium, niobium and tellurium or antimony and at least one of tantalum, tungsten, chromium, titanium, zirconium, bismuth, tin, hafnium, manganese, rhenium, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, silver, zinc, boron, aluminum, gallium, indium, germanium, lead, phosphorus, rare earth elements and alkaline earth metals. There was no suggestion to select gallium, silver and antimony over the other possible components. There was no disclosure of gold as a component of the catalyst.
U.S. Pat. No. 6,395,936 disclosed a catalyst of oxides of bismuth, tellurium, antimony, tin and/or copper and molybdenum and/or tungsten and of oxides of an alkali metal, thallium and/or samarium; an alkaline earth metal, nickel, cobalt, copper, manganese, zinc, tin, cadmium, and/or mercury; iron, chromium, cerium and/or vanadium; phosphorus, arsenic, boron and/or antimony; a rare earth metal, titanium, zirconium, niobium, tantalum, rhenium, ruthenium, rhodium, silver, gold, aluminum, gallium, indium, silicon, germanium, lead, thorium and/or uranium and molybdenum and/or tungsten. There was no suggestion to select vanadium, silver, gold, gallium, niobium and antimony over the other possible components.